JPH11131021A - Composition for coating and its laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in transparency, dyeability, various durabilities and especially weather resistance by including specific compound oxide fine particles, a silane compound and a specified epoxy(meth) acrylate therein. SOLUTION: This composition is obtained by including (A) compound oxide fine particles composed of 60-85 wt.% tin oxide, 10-30 wt.% titanium oxide and 1-10 wt.% zirconium oxide, (B) a silane compound having one or more polymerizable reactive groups, (C) an epoxy(meth)acrylate having glycidyl group and (meth)acryloyl group in one molecule at the same time and, as necessary, (D) silica fine particles having 1-100 μm particle diameter and/or a hydrolyzate and/or a partial condensate of an organosilicon compound represented by the formula Si(OR<1> )4 (R<1> is a 1-8C hydrocarbon or an alkyl). The amounts of the respective components used are preferably 20-60 wt.% component A based on the solid content and 30-70 wt.% component B and 2-30 wt.% component C respectively based on the whole composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
Provided on the above synthetic resin lens surface is a transparent coating having the same refractive index as the base material and excellent in various durability such as abrasion resistance, chemical resistance, hot water resistance, heat resistance, weather resistance, etc. To a coating composition to be coated. Further, the present invention relates to a laminate in which an antireflection film made of an inorganic substance (hereinafter referred to as an inorganic vapor deposition film) is provided on the coating.

[0002]

2. Description of the Related Art A synthetic resin lens, particularly a diethylene glycol bisallyl carbonate resin (CR-39) lens, is superior in safety, workability, fashionability, etc., as compared with a glass lens. It has spread rapidly due to the development of hard coat technology and hard coat + anti-reflection technology. However, CR-39
The refractive index of the resin is 1.50, which is lower than that of the glass lens, and the near vision lens has a disadvantage that the outer peripheral portion is thicker than the glass lens. In view of this, in the field of synthetic resin eyeglass lenses, technology development for reducing the thickness by using a high refractive index resin material has been actively performed. As technical proposals therefor, Japanese Patent Application Laid-Open Nos.
JP-A-46213 and JP-A-2-270859 propose a high-refractive-index resin material having a refractive index of 1.60 or more.

On the other hand, plastic eyeglass lenses have a drawback that they are easily damaged, and a method of providing a silicon-based hard coat film on the surface of the plastic lens is generally used. However, when the same method is applied to a high-refractive-index resin lens having a refractive index of 1.52 or more, interference fringes occur due to a difference in the refractive index between the resin lens and the coating film.
Bad appearance. As technical proposals for solving this problem, Japanese Patent Publication No. Sho 61-54331 and Japanese Patent Publication No. Sho 63-3
No. 7142, a colloidal dispersion of silicon dioxide fine particles used in a silicon-based coating composition is made of Al, Ti, Zr, Sn, Sb having a high refractive index.
A coating technique has been disclosed in which a colloidal dispersion of fine oxide particles is used. Also, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. Hei 2-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide.
-264902 discloses a technique in which fine particles obtained by treating a composite oxide of Ti, Ce and Si with an organosilicon compound are used for a coating composition.

However, none of the above-mentioned compositions for high refractive index coating which sufficiently satisfies the sufficient dyeability and various durability of the coating film itself has been obtained. Thus, Japanese Patent Application Laid-Open No. 8-31402 discloses a technique for imparting dyeability and various durability to a composition for high refractive index coating.

[0005]

Problems to be Solved by the Invention Japanese Patent Application Laid-Open No. 8-31140
The high refractive index coating composition of No. 2 secures practically no problematic levels of durability and dyeability. However, in order to further extend the service life of products to which these coating compositions have been applied, it has actually been desired to improve the level of weather resistance.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems, and found that tin oxide,
Composite oxide fine particles composed of titanium oxide and zirconium oxide, a silane compound having a polymerizable reactive group, and an epoxy (meth) acrylate having both a glycidyl group and a (meth) acryloyl group [(meth) acrylate is methacrylate And acrylate. ] A thermosetting or a photo-curing and thermo-curing of a composition containing as a main component a coating film which is excellent in transparency, and has excellent dyeability and various durability, and an inorganic vapor-deposited film is provided on the surface of the coating film. It has been found that excellent performance can be obtained in various types of durability at the same time, and that the weather resistance can be significantly improved compared with the conventional technology.

That is, the present invention is a coating composition comprising at least the following components (A), (B) and (C) as main components. (A). Composite oxide fine particles composed of tin oxide, titanium oxide, and zirconium oxide. (B). A silane compound having at least one or more polymerizable reactive groups. (C). An epoxy (meth) acrylate having both a glycidyl group and a (meth) acryloyl group in one molecule.

In the present invention, the weight percentage of the composite oxide fine particles (A) is 60-85 tin oxide, 1% titanium oxide.
A coating composition comprising 0 to 30 and zirconium oxides 1 to 10.

Further, in order to adjust the refractive index of the coating or to further improve the durability of the coating, it is possible to contain the following component (D). (D) silica fine particles having a particle size of 1 to 100 millimicrons and / or a hydrolyzate and / or partial condensate of an organosilicon compound represented by the general formula Si (OR ¹ ) ₄ (where R ¹ is 1 to 8 hydrocarbon groups and alkyl groups).

[0010] The present invention is also a laminate characterized in that an antireflection film (inorganic vapor-deposited film) made of an inorganic substance is provided on the surface of a coat film made of the coating composition.

The component (A) used in the present invention is obtained by dispersing composite oxide fine particles composed of tin oxide, titanium oxide and zirconium oxide in a dispersion medium, for example, water, alcohol, or another organic solvent in a colloidal state. It is a thing. It is also possible to use those obtained by treating the surfaces of these fine particles with an organosilicon compound, an amine compound and / or a carboxylic acid in order to enhance the dispersion stability in these coating solutions. As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. In the treatment, the hydrolyzable group may be untreated or may be hydrolyzed. After the treatment, a state in which the hydrolyzable group has reacted with the —OH group of the fine particles is preferable, but there is no problem in stability even when a part remains. As the amine compound, ammonium or ethylamine,
There are alkylamines such as triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine. The addition amount of these organosilicon compound, amine compound and carboxylic acid is 1 to 1 with respect to the weight of the fine particles.
It needs to be added within the range of about 5%. In any case, the particle diameter is preferably about 1 to 300 μm, and the kind and amount to be applied to the coating composition of the present invention are determined by the target film performance, but the amount to be used is 20 to
Desirably, it is 60% by weight. That is, if it is less than 20% by weight, the adhesion to the inorganic vapor deposition film becomes insufficient,
Alternatively, the scratch resistance of the coating film becomes insufficient. On the other hand, if it exceeds 60% by weight, cracks occur in the coating film, and the dyeability becomes insufficient.

The component (B) is a silane compound having a polymerizable reactive group such as a vinyl group, an allyl group, an acryl group, a methacryl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, and an amino group. As specific examples thereof, vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane,
Allyl trialkoxysilane, acryloxypropyl trialkoxysilane, methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxy There are silane, γ-aminopropyl trialkoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldialkoxysilane and the like.

The component (B) may be used as a mixture of two or more kinds. In addition, it is more effective to use either method after hydrolysis or use of an acid treatment on the cured film.

The amount of the component (B) used is 30 to 30% of the total composition.
Desirably, it is 70% by weight. That is, if it is less than 30% by weight, the adhesion to the inorganic vapor-deposited film tends to be insufficient. On the other hand, if it exceeds 70% by weight, cracks may occur in the cured film, which is not preferable.

Subsequently, the epoxy (meth) acrylate having a glycidyl group and a (meth) acryloyl group in one molecule of the component (C) refers to an epoxy compound having two or more glycidyl groups in a molecule. ) It is obtained by a glycidyl group ring-opening reaction with acrylic acid. Specific examples of the epoxy compound having two or more glycidyl groups in one molecule include 1,6-hexanediol glycidyl ether,
Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether,
Tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhivalate, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl Ether, diglycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether,
Diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, Alicyclic epoxy compounds such as isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcinol diglycidyl ether, bisphenol A diglycidyl ale, bisphenol F diglycidyl ether; Bisphenol S diglycidyl ether, diglycidyl orthophthalate Phenol novolak polyglycidyl ether, and aromatic epoxy compounds such as cresol novolac polyglycidyl ether.

In the present invention, the (C) component (meth) acrylate is used as a dyeing component.
1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, triglycidyl tris (2hydroxyethyl) isocyanurate Aliphatic epoxy compounds such as ethers are particularly preferred. Monocarboxylic acid-containing compounds to be reacted with these epoxy compounds include acrylic acid, methacrylic acid, and monocarboxylic acid obtained by reacting glycidyl (meth) acrylate with an acid anhydride such as O-phthalic anhydride. There are contained (meth) acrylate compounds.

The reaction between the epoxy compound and the monocarboxylic acid-containing (meth) acrylate is carried out by mixing the above compounds and using a tertiary amine compound such as dimethylaminoethyl methacrylate or a quaternary amine salt such as benzyltrimethylammonium chloride as a catalyst. In addition, it is obtained by heating to 60 to 110 ° C.

In the present invention, in addition to making the coating film tough, it is more preferable to use an epoxy (meth) acrylate having a glycidyl group and a (meth) acryloyl group simultaneously in one molecule.

This compound is obtained, for example, by reacting 1 mol of glycerol triglycidyl ether with 1.5 mol of acrylic acid.

The amount of the component (C) used is 2 to 3 of the total composition.
It must be 0% by weight. That is, if it is less than 2% by weight, the dyeing properties will be insufficient. On the other hand, if it exceeds 30% by weight, the adhesion to the inorganic vapor-deposited film tends to be insufficient,
Not preferred.

Effective examples of the silica fine particles having a particle diameter of 1 to 100 millimicrons as the component (D) include silica sol and silica fine particles. The silica sol is obtained by dispersing high molecular weight silicic acid in a colloidal state in a dispersion medium such as water, an alcohol or another organic solvent. The powdery silica fine particles are powders obtained by subjecting the surface of colloidal silica to hydrophobic treatment, and all of them are commercially available. For the purposes of this invention, an average particle size of 1 to 100
Millimicron ones are used, preferably 5 to 3
A diameter of 0 millimicron is used. If the particle diameter is less than 1 millimicron, fine silica particles do not exist stably, and constant quality cannot be obtained. On the other hand, if it is more than 100 millimicrons, there arises a problem that the coating film becomes cloudy.

The tetrafunctional silane compound represented by the general formula Si (OR ⁴ ) ₄ includes tetramethoxysilane,
Tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraaryloxysilane, tetrakis (2-methoxyethoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) ) Silane and the like. These may be used alone or as a mixture of two or more. Further, these are preferably used after being hydrolyzed in the presence of an acid in an inorganic solvent or an organic solvent such as an alcohol.

The coating composition thus obtained can be used after being diluted with a solvent, if necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers, and aromatics are used.

The coating composition of the present invention may contain, if necessary, a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, a dye for oil, a fluorescent dye, in addition to the above components. In addition, a pigment, a photochromic compound, a light- and heat-resistant stabilizer such as a hindered amine / hindered phenol compound, or the like can be added to improve the coating properties of the coating liquid and the film performance after curing.

Further, in applying the coating composition of the present invention, the surface of the substrate is previously treated with an alkali, an acid, a surfactant, an inorganic or organic material for the purpose of improving the adhesion between the substrate lens and the film. It is effective to perform a polishing treatment, a primer treatment or a plasma treatment with fine particles.

As a coating and curing method, a coating is formed by applying a coating solution by dipping, spinner, spraying or flow method and then heating and drying at a temperature of 40 to 200 ° C. for several hours. be able to. In particular, for a substrate having a heat deformation temperature of less than 100 ° C., a spinner method that does not require fixing the lens substrate with a jig is preferable.

It is also useful to add a curing catalyst for silanol or epoxy compound.

Preferred curing catalysts include chlorinated acids such as chlorinated acid, ammonium chlorate and magnesium chlorate, Cu (II), Zn (II), Co (II), Ni (II) and Be.
(II), Ce (III), Ta (III), Ti (III), Mn (II
I), La (III), Cr (III), V (III), Ci (III)
, Fe (III), Al (III), Ce (IV), Zr (IV), V
Amino acids such as acetylacetonate, amine and glycine having (IV) as the central metal atom, Lewis acids, metal salts of organic acids, and the like. Among these, preferred curing catalysts include magnesium chlorate, acetylacetonate of Al (III) and Fe (III). The addition amount is desirably in the range of 0.01 to 5.0% of the solid content.

The thickness of the cured film is 0.05
It is desirable that the thickness be 30 μm. That is, 0.05
If it is less than μm, the basic performance is not obtained, and if it exceeds 30 μm, the surface smoothness is impaired and optical distortion occurs, which is not preferable.

Examples of the coating method include a dipping method, a spray method, a roll coating method, a spin coating method and a flow coating method.

As a method of forming an antireflection film (inorganic vapor deposition film) made of an inorganic substance in the present invention, a vacuum vapor deposition method, an ion plating method, a sputtering method and the like can be mentioned. In the vacuum evaporation method, an ion beam assist method in which an ion beam is simultaneously irradiated during the evaporation may be used. As the film configuration, either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic substance used include Si
O ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ ,
Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂
O ₃ , SnO ₂ , MgF ₂ , WO and the like can be mentioned. These inorganic substances are used alone or as a mixture of two or more.

When forming the antireflection film, it is desirable to perform a surface treatment on the hard coat film. Specific examples of the steaming surface treatment include an acid treatment, an alkali treatment, an ultraviolet irradiation treatment, a plasma treatment by a high frequency discharge in an argon or oxygen atmosphere, and an ion beam irradiation treatment with argon, oxygen or nitrogen. Hereinafter, the present invention will be described in more detail with reference to examples.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail by way of examples, but the present invention is not limited thereto. Example-1 (1) Synthesis of epoxy acrylate Glycerol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd.) was placed in a 1-liter flask equipped with a thermometer and a reflux device;
While adding 754 g, 187 g of acrylic acid, 4 g of benzyltrimethylammonium chloride, 0.5 g of hydroquinone methyl ether and 235 g of butyl cellosolve under stirring and stirring at 70 ° C.
For 2 hours and at 80 ° C. for 6 hours to obtain an epoxy acrylate (EA-1). The obtained epoxy acrylate had an APHA of 150 and an oxidation of 0.05.

(2) Preparation of coating film 513.5 g of methyl cellosolve, sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (weight ratio: 76.5 / 20.5 / 3, solid content concentration 20% by weight) And 531 g of Nissan Chemical Industries, Ltd. (HIT series), and then 163 g of γ-glycidoxypropyltrimethoxysilane. 45.5 g of a 0.05N hydrochloric acid aqueous solution was added dropwise to this mixed solution with stirring, and the mixture was stirred for 3 hours and then aged for 24 hours. After adding 45 g of EA-1 to this solution, 2.6 g of aluminum acetylacetonate silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name "L")
−7001) ”and 0.9 g of a phenolic antioxidant (trade name“ Antage Crystal ”manufactured by Kawaguchi Chemical Industry Co., Ltd.), stirred for 2 hours and aged all day long to form a coating solution.

(3) Coating and Curing The coating liquid obtained in this manner was subjected to alkali treatment with a refractive index of 1.67 spectacle lens (Seiko Epson Corporation)
Co., Ltd., lens fabric for Seiko Super Sovereign). The lifting speed was 25 cm / min. After the application, the coating was dried at 80 ° C. for 20 minutes and baked at 110 ° C. for 180 minutes. The thickness of the cured film thus obtained was about 2 μm, and was excellent in both appearance and dyeability.

Example 2 An antireflection coating film made of an inorganic substance was formed on each of the lenses obtained in Example 1 by the following method. (1) Formation of anti-reflection coating After the lens obtained in Example 1 was subjected to plasma treatment (argon plasma 400 W × 60 seconds), ZrO ₂ , SiO ₂ , ZrO ₂ , SiO ₂
Was formed by a vacuum deposition method (BMC-1000, manufactured by Vacuum Instruments Co., Ltd.).
The optical film thickness of each layer was formed such that the equivalent film layer of the first ZrO ₂ layer and the SiO ₂ layer, the next ZrO ₂ layer, and the uppermost SiO ₂ layer each had γ / 4. Note that the design wavelength γ is 5
20 nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%.

(2) Test and Evaluation Results The lens obtained in Example 1 (hereinafter referred to as a hard-coated lens) and the lens obtained in Example 2 (hereinafter referred to as a hard multi-coated lens) are respectively shown below. The test was performed in the manner described, and the results are shown in Table 1.

(A) Abrasion resistance: 1 kg of Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.)
Was applied and the surface was rubbed for 10 reciprocations, and the degree of damage was visually evaluated in the following stages. A: There is no scratch in the area of 1 cm * 3 cm. B: There are 1 to 10 scratches in the above range. C: There are 10 to 100 scratches in the above range. D: Although there are countless scratches, a smooth surface remains. E: Due to scratches on the surface, no smooth surface remains.

(B) Water and chemical resistance: water, alcohol,
It was immersed in kerosene for 48 hours, and those having no change in the surface state were evaluated as good.

(C) Acid resistance and detergent resistance: 1% aqueous solution of 0.1N hydrochloric acid and 1% mama lemon (manufactured by Lion Oil & Fat Co., Ltd.)
It was immersed for 2 hours, and a material having no change in the surface condition was regarded as good.

(D) Adhesion: The adhesion between the substrate and the hard coat film and between the hard coat film and the multi-coat film is determined by JI
A cross cut tape test was performed according to SD-0202. That is, cuts are made at intervals of 1 mm on the surface of the base material using a knife, and 100 squares of 1 square mm are formed. Next, after strongly pressing a cellophane adhesive tape (trade name “Cellotape” manufactured by Nichiban Co., Ltd.) on the surface, pulling it suddenly in the direction of 90 degrees from the surface, peeling it off, and sticking with the squares remaining on the coat film Sex index.

(E) Weather resistance: A sample having no change in surface state after being exposed to a sunshine weather meter using a xenon lamp for 400 hours was evaluated as good.

(F) Abrasion resistance after weather resistance: After exposure to a sunshine weather meter using a xenon lamp for 400 hours, the same test as in (a) was performed.

(G) Durability: The durability is considered to be essentially an adhesive connection, and the cross-cut tape test described above was performed on the test items (a) to (f), and the coating film was obtained. No peeling was evaluated as good.

(H) Dyeing property (hard coat lens only): 1 g of pure water at 92 ° C. was dispersed with 2 g of Amber D, a dye for Seiko Plux diamond coating, to prepare a dyeing solution. The lens was immersed in this dyeing solution for 5 minutes, dyed, and stained without unevenness and having a total light transmittance of 30% or more between before and after dyeing.

Example 3 (1) Synthesis of Epoxy Acrylate A 1-liter flask equipped with a thermometer and a reflux condenser was charged with tripropylene glycol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd .; trade name "Denacol EX-921"). 49
2 g, 103.2 g of methacrylic acid, 3 g of benzyltrimethylammonium chloride, 0.3 g of hydroquinone methyl ether and 255.2 g of butyl cellosolve were stirred and stirred at 70 ° C. for 2 hours, at 80 ° C. for 2 hours, and then at 90 ° C. for 6 hours. The reaction was performed to obtain epoxy methacrylate (EA-2). The obtained epoxy methacrylate was APHA200, oxidation 0.05.

(2) Preparation of coating solution 1114.9 g of isopropyl cellosolve, sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (weight ratio: 80/15/5, solid content concentration 20% by weight, Nissan Chemical Industries, Ltd.) (HIT series manufactured by Corporation) 1392.
1 g, methanol-dispersed colloidal silica (trade name “Oscar 1132”, manufactured by Catalyst Chemical Industry Co., Ltd., solid content: 30)
155.1 g) and then 515.3 g of γ-glycidoxypropyltrimethoxysilane.
101 g of a 0.05N aqueous hydrochloric acid solution was added dropwise to this mixture with stirring, and the mixture was further stirred for 4 hours and then aged for 24 hours. After adding 251.7 g of EA-2 to this solution, 8.2 g of magnesium chlorate, 1.5 g of a silicon-based surfactant (trade name "L-7001" manufactured by Nippon Unicar Co., Ltd.) and a hindered amine-based photostable light 3.7 g of an agent (manufactured by Sankyo Co., Ltd., trade name "Sanol LS-770") was added, and the mixture was stirred for 4 hours and then aged all day and night to form a coating film.

(3) Coating and Curing A refractive index of 1.60 spectacle lens (manufactured by Seiko Epson Corp.,
(Lens fabric for Seiko Super Lucious). The lifting speed was 23 cm / min. After air-drying at 80 ° C for 20 minutes after application, 18 at 110 ° C
Baking was performed for 0 minutes. The thickness of the cured film thus obtained was 2 microns, and both the appearance and the dyeability were excellent.

(4) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1. Example-4 (1) Formation of an anti-reflection film After the lens obtained in Example-3 was subjected to plasma treatment (argon plasma 400 w × 60 seconds), SiO ₂ and ZrO ₂ were sequentially applied from the substrate to the atmosphere. , Si0 _2, ZrO
_An antireflection multilayer film composed of five layers of SiO ₂ and SiO ₂ was formed by a vacuum evaporation method (BMC-1000, manufactured by Vacuum Instruments Co., Ltd.). The optical film thickness of each layer is as follows: the first SiO ₂ layer, the next ZrO ₂ and SiO ₂ equivalent film layer and the next ZrO ₂ layer,
The uppermost SiO ₂ layers were each formed to have γ / 4. The design wavelength γ was 520 nm. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. The lens thus obtained was subjected to a test in the same manner as in Example 2, and the results are shown in Table 1.

Example-5 (1) Synthesis of Epoxy Methacrylate 1,1 flask was equipped with a thermometer and a reflux condenser.
-Hexanediol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd .; trade name "Denacol EX-212") 5
40 g, 170 g of methacrylic acid, 3 g of dimethylaminoethyl methacrylate, 0.3 g of hydroquinone methyl ether, and 305 g of butyl cellosolve were added, and with stirring, 70 ° C. for 2 hours, 80 ° C. for 2 hours, and then 90 ° C.
Reaction for 6 hours with epoxy methacrylate (EA-
3) was obtained. The obtained epoxy methacrylate is APH
A180, oxidation 0.05.

(2) Preparation of coating liquid 322.3 g of isopropyl cellosolve and sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (weight% ratio: 80/15/5, solid content concentration 30% by weight, Nissan Chemical Industries, Ltd.) After mixing 201 g (HIT series manufactured by Co., Ltd.), 38.4 g of γ-methacryloxypropyltrimethoxysilane, 43.8 g of γ-glycidoxypropyltrimethoxysilane and 11.8 g of tetramethoxysilane were mixed. 29.1 g of a 0.05 N hydrochloric acid aqueous solution was added dropwise to this mixed solution with stirring, and the mixture was further stirred for 3 hours and then aged for 24 hours. 53.4 EA-3 was added to this solution.
g, acetylacetone Fe (III) salt 1.1 g and a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .; trade name "L-
7604 "was added, and the mixture was stirred for 4 hours and then aged all day long to obtain a coating solution.

(3) Coating and Curing The coating liquid obtained as described above is applied to a spectacle lens having a refractive index of 1.56 (a lens fabric for Seiko Plux IIGX, manufactured by Seiko Epson Corporation) by a spinner method. Was. After air-drying at 120 ° C. for 20 minutes after the application, baking was performed at 135 ° C. for 2 hours. The thickness of the cured film thus obtained was 2.2 μm, and both the appearance and the dyeability were excellent.

(4) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

Example-6 (1) Formation of Antireflection Film After the lens obtained in Example-5 was subjected to an ion beam irradiation treatment with oxygen gas (acceleration voltage: 500 V × 60 seconds), the substrate was exposed to the atmosphere. in order Te, Si0 _2, ZrO
_{2, Si0 2, TiO 2,} SiO 2 antireflection a five-layered film vacuum deposition (manufactured by vacuum Kikai Kogyo (Co.); BMC-
1000). The optical film thickness of each layer is as follows: the first SiO ₂ layer, the equivalent film layer of the next ZrO ₂ layer and the SiO ₂ layer is γ / 4, the TiO ₂ layer is γ / 2, and the uppermost SiO ₂ layer is γ.
/ 4. The design wavelength γ is 520
nm. The obtained multilayer interference reflection film exhibited green color, and the total light transmittance was 99%.

(2) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example-2, and the results are shown in Table 1.

Comparative Example 1 A lens was coated in the same manner as in Example 1 except that EA-1 was not added. The lens thus obtained was tested in the same manner, and the results are shown in Table 1.

Comparative Example-2 In Example-5, instead of the methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite microparticle sol, a methyl cellosolve-dispersed cerium oxide-titanium oxide-silicon oxide composite microparticle sol (Catalyst Chemical Industry Co., Ltd.) Coatings were applied to the lenses in the same manner as in Example-5 except that the trade name “Optrek 1832” (solid content: 20% by weight) was used. Example 1
A test was conducted in the same manner as in Example 1 and the results are shown in Table 1.

Comparative Example 3 An antireflection film was formed on the lens obtained in Comparative Example 2 in the same manner as in Example 6. The lens thus obtained was subjected to a test in the same manner as in Example 2, and the results are shown in Table 1.

[0060]

[Table 1]

[0061]

As described above in detail, according to the present invention,
It has the same refractive index as a synthetic resin lens of 1.52 or more, and the coating film obtained by applying and curing the substrate surface is excellent in transparency, and has excellent dyeing properties, various durability, and inorganic vapor-deposited film. Provided on the surface of the coating film provided excellent performance in various durability, and in particular, with respect to the weather resistance, it was possible to greatly improve the level compared with the prior art.

A plastic material having both excellent scratch resistance, good dyeing properties, and good adhesion and durability to an antireflection film made of an inorganic material can be used for consumer or industrial purposes such as spectacle lenses and camera lenses. It can be widely applied and the effect obtained is enormous.

Claims (4)

[Claims] 1. A coating composition comprising at least the following components (A), (B) and (C) as main components. (A). Composite oxide fine particles composed of tin oxide, titanium oxide and zirconium oxide (B). A silane compound having at least one or more polymerizable reactive groups (C). Epoxy (meth) acrylate having both glycidyl and (meth) acryloyl groups in one molecule 2. The weight percentage in the composite oxide fine particles of (A).
The ratio is 60 to 85 tin oxide, 10 to 30 titanium oxide, and 1 to 10 zirconium oxide.
The coating composition according to any one of the preceding claims. 3. The coating composition according to claim 1, comprising the following component (D). (D) silica fine particles having a particle size of 1 to 100 millimicrons and / or a hydrolyzate and / or partial condensate of an organosilicon compound represented by the general formula Si (OR ¹ ) ₄ (where R ¹ is Represents a hydrocarbon group or an alkyl group of 1 to 8) 4. A laminate comprising an antireflection film made of an inorganic substance provided on the surface of a coat film made of the coating composition according to any one of claims 1 to 3.